Process for preparing 4-cyclohexyl-2-methyl-2-butanol

ABSTRACT

Process for preparing 4-cyclohexyl-2-methyl-2-butanol
         The present invention relates to a process for preparing 4-cyclohexyl-2-methyl-2-butanol. The process comprises the following steps:   a) reaction of styrene with isopropanol at elevated temperature to obtain 4-phenyl-2-methyl-2-butanol, and   b) heterogeneously catalyzed hydrogenation of 4-phenyl-2-methyl-2-butanol over a catalyst suitable for ring hydrogenation of aromatics.

The present invention relates to a process for preparing 4-cyclohexyl-2-methyl-2-butanol.

4-Cyclohexyl-2-methyl-2-butanol, which is also known as coranol, is a fragrance with a lily-of-the-valley odor, the use of which as a constituent of fragrance compositions was described for the first time in U.S. Pat. No. 4,701,278.

The preparation of 4-cyclohexyl-2-methyl-2-butanol was described by N. E. Okazawa et al. in Can. J. Chem. 60 (1982), 2180-93 and comprises the conversion of 3-cyclohexylpropanoic acid to the acid chloride, which is then reacted with 2 mol of methyllithium to give 4-cyclohexyl-2-methyl-2-butanol. Owing to the use of methyllithium, this preparation process, especially in the case of performance on a larger scale, is afflicted with not inconsiderable risks and is economically unattractive. Nevertheless, no further preparation processes have been described to date in the literature.

It is therefore an object of the present invention to provide an economically viable process for preparing 4-cyclohexyl-2-methyl-2-butanol. This object is achieved by the process described hereinafter, which comprises the following steps:

-   a) reaction of styrene with isopropanol at elevated temperature to     obtain 2-methyl-4-phenyl-2-butanol, and -   b) heterogeneously catalyzed hydrogenation of     2-methyl-4-phenyl-2-butanol over a catalyst suitable for ring     hydrogenation of aromatics.

The process can be represented by the following reaction scheme:

The invention thus relates to a process for preparing 4-cyclohexyl-2-methyl-2-butanol with the steps described here and hereinafter and in the claims.

The process is associated with a series of advantages. It allows the preparation of 4-cyclohexyl-2-methyl-2-butanol from very inexpensive commodity chemicals. The use of expensive and hazardous reagents such as methyllithium is not required. Both step a) and step b) can be performed without any problem on the industrial scale, and afford the particular products with high selectivity and good yields.

In step a) of the process according to the invention, isopropanol is reacted with styrene at elevated temperature. This forms 2-methyl-4-phenyl-2-butanol in the manner of a hydroxyalkylation, and by-products including toluene and ethylbenzene, which can, however, be removed from the target product, for example, by distillation.

In the context of an analytical study of the reaction of styrene with alkanols under supercritical conditions, the reaction was reported by T. Nakagawa et al. (see J. Supercritical Fluids, 27 (2003), p. 255-261 and Tetrahedron Lett., 48 (2007), p. 8460-8463). However, the reaction was not utilized to preparatively obtain 2-methyl-4-phenyl-2-butanol.

With regard to the selectivity of the reaction, it has been found to be advantageous when reaction in step a) is performed under supercritical conditions. This is understood to mean reaction conditions under which at least one of the components of the reaction mixture, preferably the isopropanol, is in the supercritical state. Accordingly, in a preferred embodiment of the process according to the invention, the reaction in step a) is effected under conditions under which isopropanol is in the supercritical state. The critical temperature T_(c) of isopropanol is 235° C.; the critical pressure P_(c) is 4.8 MPa. Supercritical conditions can be established by the person skilled in the art by varying pressure and temperature.

The temperature required for a sufficient rate of the reaction of styrene with isopropanol is generally at least 250° C., frequently at least 300° C. and especially at least 320° C. To achieve a sufficient selectivity of the reaction, it has been found to be advantageous when the temperature of the reaction does not exceed a value of 500° C., particularly 400° C. The reaction in step a) is effected preferably at elevated pressure, which is generally in the range from 5 to 50 MPa, frequently in the range from 10 to 30 MPa and especially in the range from 15 to 25 MPa. The pressure in the reaction vessel can be adjusted by charging with an inert substance. The reaction is preferably effected under the autogenous pressure of the reaction mixture which exists at the desired reaction temperature.

By its nature, the reaction time depends on the conditions selected and the conversion desired, and is typically in the range from 30 sec to 4 h, particularly in the range from 3 min to 3 h and especially in the range from 5 min to 2.5 h. In general, the reaction is conducted to such an extent that the reactant used in deficiency, which is preferably styrene, is converted to an extent of at least 80%, especially to an extent of at least 90%.

In one embodiment of the invention, the reaction time is in the range from 30 min to 4 h, particularly in the range from 1 to 3 h and especially in the range from 1.5 to 2.5 h. In general, the reaction is conducted to such an extent that the reactant used in deficiency, which is preferably styrene, is converted to an extent of at least 80%, especially to an extent of at least 90%.

It has been found to be particularly advantageous to perform the reaction of step a) at elevated temperatures, i.e. above 300° C., especially above 320° C., preferably in the range of 350° C. and 400° C. This allows short reaction times, which are typically in the range from 30 sec to 30 min, particularly in the range from 3 min to 20 min and especially in the range from 5 min to 15 min. In this way, even at a high styrene conversion, selectivities based on the target product of distinctly >60% can be achieved.

With regard to the selectivity of the reaction, it has been found to be advantageous when the reaction in step a) is performed in substantial or complete absence of catalysts, for example free-radical initiators, acids or transition metal compounds. “Substantial absence” means that the concentration of any catalysts is less than 1 g/kg (<1000 ppm), especially less than 0.1 g/kg (<100 ppm), based on the total weight of the reaction mixture.

The reaction of styrene with isopropanol in step a) can be performed in bulk or in a suitable diluent, i.e. one which is inert under reaction conditions. Suitable inert diluents are aprotic organic solvents which do not have an ethylenically unsaturated double bond, for example aliphatic and alicyclic ethers having preferably 4, 5 or 6 carbon atoms, aliphatic and cycloaliphatic saturated hydrocarbons having preferably 6 to 8 carbon atoms, alkyl esters of aliphatic carboxylic acids having preferably 4 to 8 carbon atoms, and mixtures of the aforementioned solvents. Preference is given to effecting the reaction in step a) in substance, i.e. essentially no feedstocks other than styrene and isopropanol, for example inert solvents, are used for the reaction. “Essentially” means here that styrene and isopropanol make up at least 95% by weight, especially at least 99% by weight, based on the total amount of the components used in step a). In addition, the reactants used for the reaction, i.e. styrene and isopropanol, as a result of the preparation, may comprise small amounts of impurities such as water, ethylbenzene, toluene and the like, in which case the impurities generally make up less than 5% by weight, especially less than 1% by weight, based on the total amount of the reactants. In particular, the water content of the reactants used in step a) is not more than 1% by weight, based on the total amount of the reactants.

With regard to the selectivity of the reaction, it has been found to be advantageous when, in the reaction in step a), isopropanol is used in a large excess, based on styrene, and/or it is ensured that a high excess of isopropanol, based on styrene present in the reaction zone, is present in the reaction zone in which styrene and isopropanol are contacted with one another under reaction conditions. In general, styrene and isopropanol are reacted in step a) in a molar ratio of styrene to isopropanol of at most 1:5, preferably at most 1:10, especially at most 1:30, more preferably at most 1:40 and especially at most 1:50. With regard to an efficient reaction regime, it is advantageous when styrene and isopropanol are used in step a) in a molar ratio in the range from 1:5 to 1:200, preferably in the range from 1:10 to 1:200, especially in the range from 1:30 to 1:150 or in the range from 1:30 to 1:130, more preferably in the range from 1:40 to 1:100 and especially in the range from 1:50 to 1:90.

The reaction in step a) can be performed in batchwise mode, i.e. styrene and isopropanol are initially charged in a suitable reactor in the desired molar ratio and brought to the desired reaction conditions and held under reaction conditions until the desired conversion. The reaction in step a) can also be performed in what is known as semibatchwise mode, i.e. the majority, generally at least 80%, of one or both reactants is introduced into the reactor under reaction conditions continuously or in portions over a prolonged period, generally at least 50% of the total reaction time. The reaction in step a) can also be performed continuously, i.e. styrene and isopropanol are fed continuously into a reaction zone in the desired molar ratio and the reaction mixture is withdrawn continuously from the reaction zone. The rate at which styrene and isopropanol are supplied to the reaction zone is guided by the desired residence time, which in turn depends in a known manner on the reactor geometry and the above-specified reaction time.

The reaction in step a) can in principle be performed in all reactors suitable for the selected reaction conditions, preferably in autoclaves, which may have apparatus for mixing of the reactants, or in reaction tubes.

In order to keep the molar ratio of styrene to isopropanol low during the reaction and simultaneously to allow an efficient reaction regime, it has been found to be advantageous when at least 80%, especially at least 90%, of the isopropanol used in step a) is initially charged, optionally together with a portion of the styrene, and at least 80%, especially at least 90%, of the styrene used in step a) is fed to the reaction in step a) under reaction conditions. The styrene can be added in portions or preferably continuously. The rate at which styrene is fed in is preferably selected such that the molar ratio of the as yet unreacted styrene fed into the reaction zone or the reactor to the isopropanol present in the reaction zone during the reaction is less than 1:10, particularly not more than 1:40 and especially not more than 1:50, for example in the range from <1:10 to 1:2000, preferably in the range from 1:40 to 1:1500 and especially in the range from 1:50 to 1:1000. In a continuous reaction regime, styrene and isopropanol will therefore preferably be supplied to the reactor or to the reaction zone in the aforementioned molar ratios. In a particular embodiment of the invention, the rate with which styrene is supplied is preferably selected such that the molar ratio of the styrene fed into the reaction zone or the reactor to the isopropanol present in the reaction zone is in the range from 1:10 to 1:130, particularly in the range from 1:20 to 1:120, more preferably in the range from 1:40 to 1:100 and especially in the range from 1:50 to 1:90. This is especially true, in the case of a continuous reaction regime too, of the molar ratios of styrene and isopropanol supplied to the reactor or to the reaction zone.

The reaction mixture obtained in step a) can be worked up in a manner known per se or be used directly as such in step b) of the process according to the invention. In general, it has been found to be advantageous to work up the reaction mixture obtained in step a), for example by extraction or distillation or by a combination of these measures. In one embodiment of the process according to the invention, the reaction mixture obtained in step a) is worked up by distillation to remove the desired 2-methyl-4-phenyl-2-butanol as the medium fraction from low and high boilers. When working with an isopropanol excess, the low boiler fraction consisting predominantly of isopropanol can be recycled into the process. In general, isopropanol will be substantially removed before step b), such that the proportion of isopropanol in the reactant used for hydrogenation in step b) is less than 20% by weight, especially not more than 10% by weight, based on the total amount of reactant in step b).

According to the configuration of the distillation, pure methyl-4-phenyl-2-butanol is obtained (purity ≧95% by weight, particularly ≧98% by weight and especially ≧99% by weight or ≧99.5% by weight), or a composition which consists essentially, i.e. to an extent of at least 95% by weight, particularly at least 98% by weight and especially at least 99% by weight or at least 99.5% by weight, of 2-methyl-4-phenyl-2-butanol and small amounts of 2-methyl-4-phenyl-2-pentanol, for example compositions in which the weight ratio of 2-methyl-4-phenyl-2-butanol to 2-methyl-4-phenyl-2-pentanol is in the range from 50:1 to 1000:1. Both the pure 2-methyl-4-phenyl-2-butanol and the composition which consists essentially of 2-methyl-4-phenyl-2-butanol and small amounts of 2-methyl-4-phenyl-2-pentanol can be used in the subsequent hydrogenation in step b), and give correspondingly pure 4-cyclohexyl-2-methyl-2-butanol (purity ≧95% by weight, particularly ≧98% by weight and especially ≧99% by weight or ≧99.5% by weight), or a composition which consists essentially, i.e. to an extent of at least 95% by weight, particularly at least 98% by weight and especially at least 99% by weight or at least 99.5% by weight of 4-cyclohexyl-2-methyl-2-butanol, and small amounts of 4-cyclohexyl-2-methyl-2-pentanol, for example compositions in which the weight ratio of 4-cyclohexyl-2-methyl-2-butanol to 4-cyclohexyl-2-methyl-2-pentanol is in the range from 50:1 to 1000:1.

The 2-methyl-4-phenyl-2-butanol obtained in step a) is subsequently subjected, in step b) of the process according to the invention, to a heterogeneously catalyzed hydrogenation over a catalyst suitable for ring hydrogenation of aromatics, which is also referred to hereinafter as catalyst.

Suitable catalysts are in principle all catalysts known to be suitable for ring hydrogenation of aromatics, i.e. catalysts which catalyze the hydrogenation of phenyl groups to cyclohexyl groups. These are typically catalysts which comprise at least one active metal from group VIIIB of the Periodic Table (CAS version), for example palladium, platinum, cobalt, nickel, rhodium, iridium, ruthenium, especially ruthenium, rhodium or nickel, or a mixture of two or more thereof, optionally in combination with one or more further active metals. Preferred further active metals are selected from groups IB and VIIB of the Periodic Table (CAS version). Among the likewise usable metals of transition groups IB and/or VIIB of the Periodic Table of the Elements, for example, copper and/or rhenium are suitable.

The catalysts may be unsupported catalysts or preferably supported catalysts. Suitable support materials are, for example, activated carbon, silicon carbide, silicon dioxide, aluminum oxide, magnesium oxide, titanium dioxide, zirconium dioxide, aluminosilicates and mixtures of these support materials. The amount of active metal is typically 0.05 to 10% by weight, frequently 0.1 to 7% by weight and especially 0.1 to 5% by weight, based on the total weight of the supported catalyst, especially when the active metal is a noble metal such as rhodium, ruthenium, platinum, palladium or iridium. In catalysts which comprise cobalt and/or nickel as active metals, the amount of active metal may be up to 100% by weight and is typically in the range from 1 to 100% by weight, especially 10 to 90% by weight, based on the total weight of the catalyst.

The supported catalysts can be used in the form of a powder. In general, such a powder has particle sizes in the range from 1 to 200 μm, especially 1 to 100 μm. Pulverulent catalysts are suitable especially when the catalyst is suspended in the reaction mixture to be hydrogenated (suspension mode). In the case of use of the catalysts in fixed catalyst beds, it is customary to use shaped bodies, which may have, for example, the shape of spheres, tablets, cylinders, strands, rings or hollow cylinders, stars and the like. The dimensions of these shaped bodies vary typically within the range from 0.5 mm to 25 mm. Frequently, catalyst extrudates with extrudate diameters of 1.0 to 5 mm and extrudate lengths of 2 to 25 mm are used. It is generally possible to achieve higher activities with smaller extrudates, but these typically do not have sufficient mechanical stability in the hydrogenation process. Therefore, very particular preference is given to using extrudates with extrudate diameters in the range from 1.5 to 3 mm. Likewise preferred are spherical support materials with sphere diameters in the range from 1 to 10 mm, especially 2 to 6 mm.

Preferred catalysts are those which comprise at least one active metal selected from ruthenium, rhodium and nickel, and optionally in combination with one or more further active metals selected from groups IB, VIIB or VIIIB of the Periodic Table (CAS version).

Particularly preferred catalysts are ruthenium catalysts. These comprise ruthenium as the active metal, optionally in combination with one or more further active metals. Preferred further active metals are selected from groups IB, VIIB or VIIIB of the Periodic Table (CAS version). The catalysts are unsupported catalysts or preferably supported catalysts. Examples of further active metals from group VIIIB are, for example, platinum, rhodium, palladium, iridium, cobalt or nickel, or a mixture of two or more thereof. Among the likewise usable metals of transition groups IB and/or VIIB of the Periodic Table of the Elements, for example, copper and/or rhenium are suitable. Preference is given to using ruthenium alone as the active metal, or together with platinum or iridium as the active metal; very particular preference is given to using ruthenium alone as the active metal.

Preference is given especially to ruthenium catalysts in which the ruthenium is arranged on support material, called supported ruthenium catalysts. The support materials of such supported catalysts generally have a BET surface area, determined by N₂ adsorption to DIN 66131, of at least 30 m²/g, especially 50 to 1000 m²/g. Preference is given to silicon dioxide-containing support materials, especially those which have a silicon dioxide content of at least 90% by weight, based on the total weight of the support material. Likewise preferred are aluminum oxide-containing support materials, especially those which have an aluminum oxide content (calculated as Al₂O₃) of at least 90% by weight, based on the total weight of the support material.

Suitable ruthenium catalysts are the catalysts specified, for example, in U.S. Pat. No. 3,027,398, DE 4407091, EP 258789, EP 813906, EP 1420012, WO 99/32427, WO 00/78704, WO 02/100536, WO 03/103830, WO 2005/61105, WO 2005/61106, WO 2006/136541, and that specified in EP 09179201.0, which was yet to be published at the priority date of the present application. With regard to the catalysts disclosed therein, reference is made to these documents.

Equally preferred catalysts are rhodium catalysts. These comprise rhodium as an active metal, optionally in combination with one or more further active metals. Preferred further active metals are selected from groups IB, VIIB or VIIIB of the Periodic Table (CAS version). The catalysts may be unsupported catalysts or preferably supported catalysts. Examples of further active metals are from the group VIIIB are, for example, platinum, palladium, iridium, cobalt or nickel, or a mixture of two or more thereof. Among the likewise useable metals of transition groups IB and/or VIIB of the Periodic Table of the Elements, copper and/or rhenium, for example, are suitable. In these catalysts, preference is given to using rhodium alone as the active metal. Suitable rhodium catalysts are known, for example, from the publications cited above for ruthenium catalysts, or can be prepared by the procedures specified therein, or are commercially available, for example the catalyst Escat 34 from Engelhard.

Equally preferred catalysts are nickel catalysts. These comprise nickel as an active metal, optionally in combination with one or more further active metals. Preferred further active metals are selected from groups IB, VIIB or VIIIB of the Periodic Table (CAS version). The catalysts may be unsupported catalysts or preferably supported catalysts. Examples of further active metals are from the group VIIIB are, for example, platinum, palladium, iridium or cobalt, or a mixture of two or more thereof. Among the likewise useable metals of transition groups IB and/or VIIB of the Periodic Table of the Elements, copper and/or rhenium, for example, are suitable. In these catalysts, preference is given to using nickel alone as the active metal. Suitable nickel catalysts are commercially available, for example BASF catalyst Ni5249P.

The catalyst used in step b) is more preferably a supported catalyst which comprises, as an active metal, ruthenium alone or together with at least one further active metal of transition groups IB, VIIB or VIIIB of the Periodic Table of the Elements (CAS version) on a support material. Preference is given to using ruthenium alone as the active metal or together with platinum or iridium as the active metal; very particular preference is given to using ruthenium alone as the active metal. Useful support materials for the supported ruthenium catalysts are in principle the aforementioned support materials. Preference is given to silicon dioxide-containing support materials, especially those which have a silicon dioxide content of at least 90% by weight, based on the total weight of the support material. Preference is likewise given to aluminum oxide-containing support materials, especially those which have an aluminum oxide content (calculated as Al₂O₃) of at least 90% by weight, based on the total weight of the support material. Preference is given to support materials having a specific BET surface area, determined by N₂ adsorption to DIN 66131, of at least 30 m²/g, especially 50 to 1000 m²/g. The amount of active metal is typically 0.05 to 10% by weight, preferably 0.1 to 3% by weight and especially 0.1 to 1% by weight, based on the total weight of the supported ruthenium catalyst.

Likewise preferably, the catalyst used in step b) is a supported catalyst which comprises, as an active metal, rhodium alone or together with at least one further active metal of transition groups IB, VIIB or VIIIB of the Periodic Table of the Elements (CAS version) on a support material. Preference is given to using rhodium alone as the active metal or together with platinum or iridium as the active metal; very particular preference is given to using rhodium alone as the active metal. Useful support materials for the supported rhodium catalysts are in principle the aforementioned support materials. Preference is given to silicon dioxide-containing support materials, especially those which have a silicon dioxide content of at least 90% by weight, based on the total weight of the support material. Preference is likewise given to aluminum oxide-containing support materials, especially those which have aluminum oxide content (calculated as Al₂O₃) of at least 90% by weight, based on the total weight of the support material. The amount of active metal is typically 0.05 to 10% by weight, based on the total weight of the supported rhodium catalyst.

Likewise preferably, the catalyst used in step b) is a catalyst which comprises, as an active metal, nickel alone or together with at least one further active metal of transition groups IB, VIIB or VIIIB of the Periodic Table of the Elements (CAS version), optionally on a support material. Preference is given to using nickel alone as the active metal.

Useful support materials for the supported nickel catalysts are in principle the aforementioned support materials. Preference is given to silicon dioxide-, aluminum oxide- and magnesium oxide-containing support materials, especially those which consist to an extent of at least 90% by weight of such materials. The amount of active metal is typically 1 to 90% by weight, preferably 10 to 80% by weight and especially 30 to 70% by weight, based on the total weight of the supported nickel catalyst. Preference is also given to those nickel catalysts which consist essentially exclusively of active metal, i.e. wherein the amount of active metal is more than 90% by weight, e.g. 90 to 100% by weight.

In a particularly preferred embodiment, a shell catalyst is used, especially a shell catalyst which has, as the active metal, ruthenium alone or together with at least one further active metal of transition groups IB, VIIB or VIIIB of the Periodic Table of the Elements in the amounts specified above. Such shell catalysts are known especially from WO 2006/136541, and in EP 09179201.0, which was yet to be published at the priority date of the present application.

Such a shell catalyst is a supported catalyst wherein the predominant amount of the active metal(s) present in the catalyst is close to the surface of the catalyst. In particular, at least 60% by weight, more preferably at least 80% by weight, based in each case on the total amount of the active metal, is present down to a penetration depth of not more than 200 μm, i.e. in a shell with a distance of not more than 200 μm from the surface of the catalyst particles. In contrast, only a very small amount, if any, of the active metal is present in the interior (core) of the catalyst. Very particular preference is given to an inventive shell catalyst in which no active metal can be detected in the interior of the catalyst, i.e. active metal is present only in the outermost shell, for example in a zone down to a penetration depth of 100 to 200 μm. The aforementioned data can be determined by means of SEM (scanning electron microscopy), EPMA (electron probe microanalysis)-EDXS (energy dispersive X-ray spectroscopy), and are averaged values. Further data with regard to the aforementioned test methods and techniques can be found, for example, in “Spectroscopy in Catalysis” by J. W. Niemantsverdriet, VCH, 1995. For further details regarding the penetration depth of active metal, reference is made to WO 2006/136541, especially to page 7 lines 6 to 12.

Preferred shell catalysts have a content of active metal in the range from 0.05 to 1% by weight, especially 0.1 to 0.5% by weight, more preferably 0.25 to 0.35% by weight, based in each case on the total weight of the catalyst.

For the inventive hydrogenation in step b), particular preference is given to shell catalysts with a support material based on silicon dioxide, generally amorphous silicon dioxide. The term “amorphous” in this context is understood to mean that the proportion of crystalline silicon dioxide phases makes up less than 10% by weight of the support material. The support materials used to prepare the catalysts may, however, have superstructures which are formed via regular arrangement of pores in the support material. Useful support materials are in principle amorphous silicon dioxide types which consist at least to an extent of 90% by weight of silicon dioxide, where the remaining 10% by weight, preferably not more than 5% by weight, of the support material may also be another oxidic material, for example MgO, CaO, TiO₂, ZrO₂, Fe₂O₃ and/or alkali metal oxide. In a preferred embodiment of the shell catalyst, the support material is halogen-free, especially chlorine-free, i.e. the content of halogen in the support material is less than 500 ppm by weight, for example in the range from 0 to 400 ppm by weight. Thus, a preferred shell catalyst is one which comprises less than 0.05% by weight of halide (determined by ion chromatography), based on the total weight of the catalyst. Preference is given to support materials which have a specific surface area in the range from 30 to 700 m²/g, preferably 30 to 450 m²/g (BET surface area to DIN 66131). Suitable amorphous support materials based on silicon dioxide are familiar to those skilled in the art and are commercially available (see, for example, O. W. Flörke, “Silica” in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition on CD-ROM). They may either be of natural origin or may have been produced synthetically. Examples of suitable amorphous support materials based on silicon dioxide are silica gels, kieselguhr, fumed silicas and precipitated silicas. In a preferred embodiment of the invention, the catalysts have silica gels as support materials. According to the configuration of the shell catalyst, the support material may have different shapes. When the process in which the inventive shell catalysts are used is configured as a suspension process, the inventive catalysts will typically be prepared using the support material in the form of a fine powder. The powder preferably has particle sizes in the range from 1 to 200 μm, especially 1 to 100 μm. In the case of use of the inventive shell catalyst in fixed catalyst beds, it is customary to use shaped bodies of the support material, which are obtainable, for example, by extrusion or tableting, and which may have, for example, the form of spheres, tablets, cylinders, extrudates, rings or hollow cylinders, stars and the like. The dimensions of these shaped bodies typically vary within the range from 0.5 mm to 25 mm. Frequently, catalyst extrudates with extrudate diameters of 1.0 to 5 mm and extrudate lengths of 2 to 25 mm are used. It is generally possible to achieve higher activities with smaller extrudates; these, however, often do not have sufficient mechanical stability in the hydrogenation process. Therefore, very particular preference is given to using extrudates with extrudate diameters in the range from 1.5 to 3 mm. Preference is likewise given to spherical support materials with sphere diameters in the range from 1 to 10 mm, especially 2 to 6 mm.

In a particularly preferred embodiment of the shell catalysts, the support material of the catalyst, which is especially a support material based on silicon dioxide, has a pore volume in the range from 0.6 to 1.0 ml/g, preferably in the range from 0.65 to 0.9 ml/g, for example 0.7 to 0.8 ml/g, determined by Hg porosimetry (DIN 66133), and a BET surface area in the range from 280 to 500 m²/g, preferably in the range from 280 to 400 m²/g, most preferably in the range from 300 to 350 m²/g. In such shell catalysts, at least 90% of the pores present preferably have a diameter of 6 to 12 nm, preferably 7 to 11 nm, more preferably 8 to 10 nm. The pore diameter can be determined by processes known to those skilled in the art, for example by Hg porosimetry or N₂ physisorption. In a preferred embodiment, at least 95%, more preferably at least 98%, of the pores present have a pore diameter of 6 to 12 nm, preferably 7 to 11 nm, more preferably 8 to 10 nm. In a preferred embodiment, no pores smaller than 5 nm are present in these shell catalysts. Furthermore, there are preferably no pores larger than 25 nm, especially larger than 15 nm, in these shell catalysts. In this composition, “no pores” means that no pores with these diameters can be found by customary test methods, for example Hg porosimetry or N₂ physisorption.

In preferred shell catalysts, the dispersity of the active metal is preferably 30 to 60%, more preferably 30 to 50%. Processes for measuring the dispersity of the active metal are known per se to those skilled in the art, for example by pulse chemisorption, the determination of the noble metal dispersion (specific metal surface area, crystal size) being carried out by the CO pulse method (DIN 66136(1-3)).

The hydrogenation process according to the invention can be performed in the liquid phase or in the gas phase. Preference is given to performing the hydrogenation process according to the invention in the liquid phase.

The hydrogenation process according to the invention can be performed in the absence of a solvent or diluent or in the presence of a solvent or diluent, i.e. it is not necessary to perform the hydrogenation in solution. The solvent or diluent used may be any suitable solvent or diluent. Useful solvents or diluents are in principle those which are capable of very substantially dissolving the organic compounds to be hydrogenated, or mix completely therewith, and which are inert under the hydrogenation conditions, i.e. are not hydrogenated. Examples of suitable solvents are cyclic and acyclic ethers having preferably 4 to 8 carbon atoms, for example tetrahydrofuran, dioxane, methyl tert-butyl ether, dimethoxyethane, dimethoxypropane, dimethyldiethylene glycol, aliphatic alcohols having preferably 1 to 6 carbon atoms, such as methanol, ethanol, n- or isopropanol, n-, 2-, iso- or tert-butanol, carboxylic esters of aliphatic carboxylic acids having preferably 3 to 8 carbon atoms, such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and aliphatic ether alcohols such as methoxypropanol, and cycloaliphatic compounds such as cyclohexane, methylcyclohexane and dimethylcyclohexane. The amount of the solvent or diluent used is not particularly restricted and can be selected freely as required, although, when using a solvent, preference is given to those amounts which lead to a 3 to 70% by weight solution of the organic compound intended for hydrogenation.

In one embodiment of the invention, step b) of the invention is performed in substance.

The actual hydrogenation is effected typically in analogy to the known hydrogenation processes for hydrogenating organic compounds which have hydrogenatable groups, preferably for hydrogenating a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, as described in the prior art cited at the outset. For this purpose, the organic compound as a liquid phase or gas phase, preferably as a liquid phase, is contacted with the catalyst in the presence of hydrogen. The liquid phase can be passed over a moving catalyst bed (moving bed mode) or a fixed catalyst bed (fixed bed mode).

The hydrogenation can be configured either continuously or batchwise, preference being given to the continuous process regime. The process according to the invention is preferably performed in trickle reactors or in flooded mode by the fixed bed mode, particular preference being given to performance in trickle reactors. More particularly, the compound to be hydrogenated here is used in substance, i.e. substantial absence of organic diluents (solvent content preferably <10%). The hydrogenation can be passed over the catalyst either in cocurrent with the solution of the reactant to be hydrogenated or in countercurrent. The hydrogenation can also be performed batchwise in batchwise mode. In this case, the hydrogenation will preferably be performed in an organic solvent or diluent.

In the case of batchwise performance of the process according to the invention, in step B, the catalyst is typically used in an amount such that the concentration of ruthenium in the reaction mixture used for hydrogenation is in the range from 10 to 10 000 ppm, especially in the range from 50 to 5000 ppm, especially in the range from 100 to 1000 ppm.

The hydrogenation is effected typically at a hydrogen pressure in the range from 5 to 50 MPa, especially in the range from 10 to 30 MPa. The hydrogen can be fed into the reactor as such, or diluted with an inert, for example nitrogen or argon.

The hydrogenation in step b) is effected typically at temperatures above 50° C., especially in the range from 100 to 250° C.

Apparatus suitable for performing the hydrogenation is known to those skilled in the art and is guided primarily by the mode of operation. Suitable apparatus for performing a hydrogenation according to the hydrogenation over a moving catalyst bed and over a fixed catalyst bed are known, for example, from Ullmanns Enzyklopädie der Technischen Chemie, 4th edition, volume 13, p. 135 ff., and from P. N. Rylander, “Hydrogenation and Dehydrogenation” in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. on CD-ROM.

It has been found that, surprisingly, step a) of the process according to the invention affords not only 2-methyl-4-phenyl-2-butanol but also a small amount of 2-methyl-4-phenyl-2-pentanol when it is performed under conditions under which isopropanol is present under supercritical conditions, especially when the molar ratio of styrene to isopropanol is in the range from 1:10 to 1:130, particularly in the range from 1:30 to 1:120, more preferably in the range from 1:40 to 1:100 and especially in the range from 1:50 to 1:90, and/or when the reaction is performed in semibatchwise mode.

Such a process is novel and likewise forms part of the subject matter of the present invention. Accordingly, the invention relates to a process for preparing a composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol, comprising the reaction of styrene with isopropanol at elevated temperature under conditions under which isopropanol is present under supercritical conditions, the molar ratio of styrene to isopropanol being in the range from 1:10 to 1:130 particularly in the range from 1:30 to 1:120, more preferably in the range from 1:40 to 1:100 and especially in the range from 1:50 to 1:90.

It has been found to be advantageous when the reaction is performed in semibatchwise mode or continuously, as already described above for step a). For this purpose, it has been found to be especially advantageous when at least 80%, especially at least 90%, of the isopropanol used is initially charged, optionally together with a portion of the styrene, and at least 80%, especially at least 90%, of the styrene used is supplied to the reaction under reaction conditions. The styrene can be added in portions or preferably continuously. The rate with which the styrene is supplied is preferably selected such that the molar ratio of the styrene fed into the reaction zone or the reactor to the isopropanol present in the reaction zone is in the range from 1:10 to 1:130, particularly in the range from 1:20 to 1:120, more preferably in the range from 1:40 to 1:100 and especially in the range from 1:50 to 1:90. This is especially true, in a continuous reaction regime too, of the molar ratios of styrene and isopropanol supplied to the reactor or to the reaction zone.

Otherwise, the conditions specified above for step a) also apply in the same way to the process according to the invention for preparing a composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol. Reference is therefore made to these details in full.

Such a process affords compositions which comprise 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol. The weight ratio of 2-methyl-4-phenyl-2-butanol to 2-methyl-4-phenyl-2-pentanol in such compositions is typically in the range from 50:1 to 1000:1.

The reaction mixture obtained in the preparation of a composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol by reaction of styrene with isopropanol can be worked up in the manner described above for step a). Reference is made completely to the details given above for workup of the reaction mixture obtained in step a). More particularly, the reaction mixture obtained is worked up by distillation, in which case the desired composition consisting essentially of 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol is removed as the middle fraction from low and high boilers. In general, a composition is then obtained which consists essentially, i.e. to an extent of at least 95% by weight, particularly at least 98% by weight and especially at least 99% by weight or at least 99.5% by weight of 2-methyl-4-phenyl-2-butanol, and small amounts of 2-methyl-4-phenyl-2-pentanol, for example compositions in which the weight ratio of 2-methyl-4-phenyl-2-butanol to 2-methyl-4-phenyl-2-pentanol in the range from 50:1 to 1000:1.

Such mixtures of 2-methyl-4-phenyl-2-butanol and small amounts of 2-methyl-4-phenyl-2-pentanol can subsequently be hydrogenated in analogy to step b) to obtain compositions comprising 4-cyclohexyl-2-methyl-2-butanol and small amounts of 4-cyclohexyl-2-methyl-2-pentanol, for example compositions in which the weight ratio of 4-cyclohexyl-2-methyl-2-butanol to 4-cyclohexyl-2-methyl-2-pentanol is in the range from 50:1 to 1000:1. Reference is made completely to the details given above for the hydrogenation in step b). Since an isopropanol excess can be employed in the preparation of a composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol, the low boiler fraction, which consists predominantly of isopropanol, can be recycled into the process. In general, isopropanol will be substantially removed before the hydrogenation, such that the proportion of isopropanol in the reactant used for the hydrogenation is less than 20% by weight, especially not more than 10% by weight, based on the total amount of reactant.

Compositions comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol are surprisingly notable in that they have a more flowery odor note compared to 2-methyl-4-phenyl-2-butanol. Such compositions are novel and likewise form part of the subject matter of the invention. In these compositions, the weight ratio of 2-methyl-4-phenyl-2-butanol to 2-methyl-4-phenyl-2-pentanol is in the range from 50:1 to 1000:1. A specific composition is that of concentrates, i.e. compositions which consist essentially, i.e. to an extent of at least 95% by weight, particularly at least 98% by weight and especially at least 99% by weight or at least 99.5% by weight of 2-methyl-4-phenyl-2-butanol and small amounts of 2-methyl-4-phenyl-2-pentanol, for example compositions in which the weight ratio of 2-methyl-4-phenyl-2-butanol to 2-methyl-4-phenyl-2-pentanol is in the range from 50:1 to 1000:1. Compositions in which the weight ratio of 2-methyl-4-phenyl-2-butanol to 2-methyl-4-phenyl-2-pentanol is outside the range specified here can be prepared by mixing 2-methyl-4-phenyl-2-butanol (Muguet alcohol) with the desired amount of 2-methyl-4-phenyl-2-pentanol. Such compositions of course likewise form part of the subject matter of the present invention.

Such compositions, especially the aforementioned concentrates, can be used as fragrances or aromas for the reasons mentioned above, especially in cosmetic compositions and in washing or cleaning compositions.

The invention therefore also provides cosmetic compositions which comprise a composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol.

The invention therefore also provides washing or cleaning compositions which comprise a composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol.

It has additionally been found in the context of this invention that 2-methyl-4-phenyl-2-pentanol can also be prepared in a controlled manner by reacting α-methylstyrene with isopropanol under the conditions specified above for step a).

The invention therefore also provides a process for preparing 2-methyl-4-phenyl-2-pentanol, in which α-methylstyrene is reacted with isopropanol at elevated temperature. For the reaction of α-methylstyrene with isopropanol, essentially all details apply which have been given above and in the claims for the reaction of styrene with isopropanol in step a). Reference is therefore made completely to these details.

Alternatively, 2-methyl-4-phenyl-2-pentanol or a mixture consisting essentially of 2-methyl-4-phenyl-2-pentanol can be obtained by distillative separation of mixtures comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol, for example by distillative separation of mixtures as obtained in step a) of the process according to the invention.

2-Methyl-4-phenyl-2-pentanol is likewise an odorant and can therefore be used in all applications for odorants of this type. As already stated above, it can surprisingly also be used for modification of the odor properties of 2-methyl-4-phenyl-2-butanol. The use of 2-methyl-4-phenyl-2-pentanol as an odorant has not been described to date. It therefore likewise forms part of the subject matter of the present invention, more particularly the use of 2-methyl-4-phenyl-2-pentanol as an odorant in cosmetic compositions and in washing or cleaning compositions.

The invention therefore also provides cosmetic compositions comprising 2-methyl-4-phenyl-2-pentanol.

The invention therefore also provides washing or cleaning compositions comprising 2-methyl-4-phenyl-2-pentanol.

2-Methyl-4-phenyl-2-pentanol can be subjected to a hydrogenation in analogy to step b). This gives 4-cyclohexyl-2-methyl-2-pentanol in a high yield.

4-Cyclohexyl-2-methyl-2-pentanol is novel and likewise forms part of the subject matter of the present invention.

4-Cyclohexyl-2-methylpentanol is, similarly to 4-cyclohexyl-2-methyl-2-butanol, an odorant. In addition, it can surprisingly be used for modification of the odor properties of other odorants, especially of 4-cyclohexyl-2-methyl-2-butanol. 4-Cyclohexyl-2-methyl-2-pentanol can therefore be used as a fragrance or aroma, especially in cosmetic compositions and in washing or cleaning compositions.

The invention therefore also provides cosmetic compositions comprising 4-cyclohexyl-2-methyl-2-pentanol.

The invention therefore also provides washing or cleaning compositions comprising 4-cyclohexyl-2-methyl-2-pentanol.

Compositions which comprise 4-cyclohexyl-2-methyl-2-butanol and 4-cyclohexyl-2-methyl-2-pentanol are surprisingly notable in that, compared with 4-cyclohexyl-2-methyl-2-butanol, they have a more flowery odor note. Such compositions are novel and likewise form part of the subject matter of the invention.

In these compositions, the weight ratio of 4-cyclohexyl-2-methyl-2-butanol to 4-cyclohexyl-2-methyl-2-pentanol is generally in the range from 50:1 to 1000:1. Such compositions may also comprise small amounts of 4-cyclohexyl-2-methylbutane and possibly 4-cyclohexyl-2-methylpentane, which are obtained by over-reduction of 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol respectively. The proportion by weight of the total amount of cyclohexyl-2-methylbutane and any 4-cyclohexyl-2-methylpentane will generally not exceed 10% by weight, especially 5% by weight, based on 4-cyclohexyl-2-methyl-2-butanol, and is, if present, in the range from 0.01 to 10% by weight, especially in the range from 0.01 to 5% by weight, based on 4-cyclohexyl-2-methyl-2-butanol. It is of course also possible to remove cyclohexyl-2-methylbutane and any 4-cyclohexyl-2-methylpentane, for example by a distillative route, such that the total amount of cyclohexyl-2-methylbutane and any 4-cyclohexyl-2-methylpentane is less than 1% by weight, especially less than 0.5% by weight or less than 0.1% by weight, based on 4-cyclohexyl-2-methyl-2-butanol. A specific composition is that of concentrates, i.e. compositions which consist essentially, i.e. to an extent of at least 95% by weight, particularly at least 98% by weight and especially at least 99% by weight or at least 99.5% by weight of 4-cyclohexyl-2-methyl-2-butanol and small amounts of 4-cyclohexyl-2-methyl-2-pentanol, for example compositions in which the weight ratio of 4-cyclohexyl-2-methyl-2-butanol to 4-cyclohexyl-2-methyl-2-pentanol is in the range from 50:1 to 1000:1.

These concentrates may comprise cyclohexyl-2-methylbutane and possibly 4-cyclohexyl-2-methylpentane in the amounts mentioned above. Compositions in which the weight ratio of 4-cyclohexyl-2-methyl-2-butanol to 4-cyclohexyl-2-methyl-2-pentanol is outside the range specified here can be prepared by mixing cyclohexyl-2-methyl-2-butanol with the desired amount of 4-cyclohexyl-2-methyl-2-pentanol. Such compositions of course likewise form part of the subject matter of the present invention.

Such compositions, especially the aforementioned concentrates, can be used as fragrances or aromas for the reasons mentioned above, especially in cosmetic compositions and in washing or cleaning compositions.

The invention therefore also provides cosmetic compositions which comprise a composition comprising 4-cyclohexyl-2-methyl-2-butanol and 4-cyclohexyl-2-methyl-2-pentanol.

The invention therefore also provides washing or cleaning compositions which comprise a composition comprising 4-cyclohexyl-2-methyl-2-butanol and 4-cyclohexyl-2-methyl-2-pentanol.

As already stated above, 4-cyclohexyl-2-methyl-2-pentanol can be prepared from 2-methyl-4-phenyl-2-pentanol in analogy to step b), i.e. by a process comprising a heterogeneously catalyzed hydrogenation of 2-methyl-4-phenyl-2-pentanol over a catalyst suitable for ring hydrogenation of aromatics. Such a process likewise forms part of the subject matter of the present invention. With regard to the hydrogenation of 2-methyl-4-phenyl-2-pentanol, reference is made completely to the details given above for the hydrogenation in step b).

The procedure here may be first to prepare 2-methyl-4-phenyl-2-pentanol in a controlled manner and then to subject it to a heterogeneously catalyzed hydrogenation over a catalyst suitable for ring hydrogenation of aromatics, in analogy to step b) described above.

However, the procedure may also be first to prepare a composition composed of 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol, for example in the manner described above for step a), to subject this composition to a heterogeneously catalyzed hydrogenation over a catalyst suitable for ring hydrogenation of aromatics in analogy to the above-described step b), and to separate the composition obtained, which comprises 4-cyclohexyl-2-methyl-2-butanol and 4-cyclohexyl-2-methyl-2-pentanol, into its constituents by distillation.

Accordingly, the invention also relates to a process for preparing 4-cyclohexyl-2-methyl-2-pentanol, comprising the following steps:

-   a′) preparation of a composition comprising     2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol by     reaction of styrene with isopropanol at elevated temperature under     conditions under which isopropanol is present under supercritical     conditions, the molar ratio of styrene to isopropanol being in the     range from 1:10 to 1:130; -   b′) heterogeneously catalyzed hydrogenation of the composition     obtained in step a) over a catalyst suitable for ring hydrogenation     of aromatics; and -   c) distillative workup of the composition obtained in step b′) to     obtain a composition consisting essentially, i.e. to an extent of at     least 90% by weight, especially to an extent of at least 95% by     weight, of 4-cyclohexyl-2-methyl-2-pentanol.

Accordingly, the invention further relates to a process for preparing 4-cyclohexyl-2-methyl-2-pentanol, comprising the following steps:

-   a′) preparation of a composition comprising     2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol by     reaction of styrene with isopropanol at elevated temperature under     conditions under which isopropanol is present under supercritical     conditions, the molar ratio of styrene to isopropanol being in the     range from 1:10 to 1:130; -   c′) distillative workup of the composition obtained in step a′) to     obtain a composition consisting predominantly of     2-methyl-4-phenyl-2-pentanol -   b′) heterogeneously catalyzed hydrogenation of the composition     obtained in step c′) over a catalyst suitable for ring hydrogenation     of aromatics; and optionally -   c″) distillative workup of the composition obtained in step b′) to     obtain a composition consisting essentially of     4-cyclohexyl-2-methyl-2-pentanol.

It will be appreciated that step a′) is performed in analogy to the step a) already described above. To that extent, for step a′), reference is made completely to the details given for step a).

It will also be appreciated that step b′) is performed in analogy to the step ab) already described above. To that extent, for step b′), reference is made completely to the remarks made for step b).

The distillative steps c), c′) and c″) can be performed in analogy to customary processes for fractional distillation. Suitable apparatus for this purpose is familiar to those skilled in the art. The necessary conditions can be determined by routine experiments. In general, distillation is effected under reduced pressure.

In addition, the invention additionally relates to a process for preparing 4-cyclohexyl-2-methyl-2-pentanol, comprising the following steps:

-   a″) reaction of α-methylstyrene with isopropanol at elevated     temperature to obtain 2-methyl-4-phenyl-2-pentanol, and -   b″) heterogeneously catalyzed hydrogenation of     2-methyl-4-phenyl-2-pentanol over a catalyst suitable for ring     hydrogenation of aromatics.

As already explained above, step a″) is performed in analogy to the step a) already described above. To that extent, for step a″), reference is made completely to the details given for step a).

It will also be appreciated that step b″) is performed in analogy to the step ab) already described above. To that extent, for step b″), reference is made completely to the details given for step b).

It will also be appreciated that the reaction product obtainable in step a″), before use thereof in step b″), can be subjected to a workup in analogy to that for the reaction product obtained in step a) above, especially to a distillative workup in which low boilers and high boilers are removed, and 2-methyl-4-phenyl-2-pentanol is obtained as a medium boiler. In this regard, reference is likewise made to the details given above.

As already stated above, the invention also relates to cosmetic compositions which comprise one of the following substances or substance mixtures as fragrances or aromas:

-   i. 4-cyclohexyl-2-methyl-2-pentanol; -   ii. 2-methyl-4-phenyl-2-pentanol; -   iii. composition comprising 2-methyl-4-phenyl-2-butanol and     2-methyl-4-phenyl-2-pentanol; or -   iv. composition comprising 4-cyclohexyl-2-methyl-2-butanol and     4-cyclohexyl-2-methyl-2-pentanol.

Examples of suitable cosmetic compositions are in principle all cosmetic compositions which typically comprise fragrances. These include, for example, eau de parfum, eau de toilette, eau de cologne, aftershave products such as lotions and creams, preshave products, perfumed wet wipes, hair removal creams and lotions, tanning creams and lotions, haircare products such as shampoos, hair rinses, hairsetting products, hair gels, hair tints, hair waxes, hair sprays, setting foams, hair mousses, split end fluids, neutralizing agents for permanent waves, hair dyes and bleaches or hot oil treatments, and also skin cleansing products such as soaps, washing gels, shower gels, bodycare products such as creams, oils, lotions and the like for skin, especially products for care of the hands, of the face and of the feet, sunscreens, deodorants and antiperspirants, skin disinfectants, insect repellents and decorative cosmetic products. According to the field of use, the cosmetic compositions may be formulated as aqueous or alcoholic liquid, oil, (aerosol) spray, (aerosol) foam, mousse, gel, gel spray, cream, lotion, powder, tabs or wax.

As already stated above, the invention also relates to washing or cleaning compositions which comprise one of the following substances or substance mixtures as fragrances or aromas:

-   i. 4-cyclohexyl-2-methyl-2-pentanol; -   ii. 2-methyl-4-phenyl-2-pentanol; -   iii. composition comprising 2-methyl-4-phenyl-2-butanol and     2-methyl-4-phenyl-2-pentanol; or -   iv. composition comprising 4-cyclohexyl-2-methyl-2-butanol and     4-cyclohexyl-2-methyl-2-pentanol.

These include products for cleaning and/or disinfection of surfaces, for example household cleaners, neutral cleaners, toilet cleaners, floor cleaners, carpet cleaners, window cleaners, polishes, furniture care products, liquid and solid dishwashing products, liquid and solid machine dishwashing products, and also products for cleaning or treatment of textiles, such as solid or liquid textile washing compositions, laundry aftertreatment compositions, fabric softeners, ironing aids, textile fresheners, fabric preconditioners, washing soaps, washing tablets and the like.

In addition, the inventive substances and substance mixtures can be used as a fragrance constituent in other fragrance-containing products, such as air conditioners, lamp oils, candles, air fresheners and the like.

The invention is illustrated in detail by the examples which follow:

PREPARATION EXAMPLE 1 Preparation of the Hydrogenation Catalyst

The support material used was a spherical SiO₂ support (AF125 type from BASF SE) with a sphere diameter of 3 to 5 mm and a tapped density of 0.49 kg/I. The BET surface area was 337 m²/g, and the water absorption (WA) 0.83 ml/g. For impregnation, 14.25% by weight ruthenium(III) acetate solution in acetic acid from Umicore was used.

200 g of support were initially charged in a round-bottom flask. 15 g of ruthenium acetate solution were diluted with distilled water to 150 ml (90% WA). The support material was initially charged in the distillation flask of a rotary evaporator, and the first quarter of the solution was pumped onto the support material at 3 to 6 rpm with a slightly reduced pressure. On completion of the addition, the support was left in the rotary evaporator at 3 to 6 rpm for a further 10 minutes, in order to homogenize the catalyst. This impregnation-homogenization step was repeated three times more until all of the solution had been applied to the support. The support material thus treated was dried while being agitated in the rotary tube oven at 140° C., then reduced in a hydrogen stream (20 l/h of H₂; 10 l/h of N₂) at 200° C. for 3 h, and passivated at 25° C. (5% air in N₂, 2 h). The inventive catalyst A thus obtained comprised 0.34% by weight of ruthenium, based on the catalyst weight.

Step a EXAMPLE 1

A 400 ml autoclave was initially charged with 2.08 g (20.0 mmol) of styrene and 51.2 g (853 mmol) of isopropanol. The autoclave was closed and the reaction mixture was stirred at 350° C. (autogenous pressure 230 bar). After a reaction time of 2 h in each case, another 2.08 g (20.0 mmol) of styrene were added. After a total of 14 additions, corresponding to a total amount of styrene of 31.2 g (300 mmol), the reaction mixture was allowed to cool, and the autoclave was decompressed. Before each addition, a sample was taken and analyzed by means of gas chromatography for the composition thereof. In this way, the selectivity of the formation of 2-methyl-4-phenyl-2-butanol was determined based on the styrene used. The selectivities are reported in the table which follows:

Styrene [mmol] 40 80 120 160 200 240 280 300 Reaction time 4 8 12 16 20 24 28 30 [h] Selectivity [%] 90.0 81.8 77.3 70.9 67.9 63.9 59.6 57.3

The reaction mixture was worked up by distillation. After removing the low boilers (in particular isopropanol), a crude product of purity >75% was obtained, which also comprised 2-methyl-4-phenyl-2-pentanol (1.0 GC area %). Further fine distillation gave 25.7 g (0.151 mol) of 4-phenyl-2-methylbutan-2-ol, corresponding to a yield of 50.3%.

A mixture of 2-methyl-4-phenyl-2-butanol (99.8%) and 2-methyl-4-phenyl-2-pentanol (0.11 GC area %) obtained in the fine distillation was notable, in terms of odor, especially for an additional pleasant, faintly flowery note compared to the pure substance 2-methyl-4-phenyl-2-butanol.

EXAMPLE 2

A 400 ml autoclave was additionally charged with 118 g (1.96 mol) of isopropanol. The autoclave was closed and brought to internal temperature 375° C. (autogenous pressure 244 bar). 2.06 g (19.8 mmol) of styrene were added rapidly thereto and, after 15 min of reaction time, another 2.08 g (20.0 mmol) of styrene were added thereto. Styrene was added in this way four more times. After a total of 6 additions, corresponding to a total amount of styrene of 12.36 g (119 mmol), the reaction mixture was allowed to cool and then the autoclave was decompressed. Before each addition, a sample was taken and analyzed by means of gas chromatography for the composition thereof. In this way, the selectivity of the formation of 2-methyl-4-phenyl-2-butanol based on the styrene used was determined. The selectivities are reported in the following table:

Styrene [mmol] 19.8 38.6 59.4 79.2 99 118.8 Reaction time 15 30 45 60 75 90 [min] Selectivity [%] 72.1 62.5 65.5 65.1 65.2 63.6

EXAMPLE 3 Continuous Mode

A 300 ml autoclave was initially charged with 78 g of isopropanol. The autoclave was closed and the reaction mixture was heated to internal temperature 350° C. (autogenous pressure 150 bar). Subsequently, continuous dosage and withdrawal were effected under pressure control, such that pressure and temperature always remained constant. A mixture of styrene and isopropanol in a ratio of 1:10 (parts by weight) was metered in at a flow rate of 40 g/h. Correspondingly, an output of 40 g/h was withdrawn from the reactor.

The course of the reaction was monitored by means of gas chromatography. A steady state was established in the reactor after approx. 10 h. The styrene conversion was determined to be 75%, and an output of 2-methyl-4-phenyl-2-butanol of 2 g/h was found.

EXAMPLE 4

A 400 ml autoclave was initially charged with 51.2 g (853 mmol) of isopropanol. The autoclave was closed and the contents were stirred at 350° C. (autogenous pressure 230 bar). A metering pump was used to add styrene to the autoclave at an addition rate of 1.04 g/h (10 mmol/h) over a period totaling 20 h. Subsequently, the reaction mixture was allowed to cool and the autoclave was decompressed. Samples were taken at intervals of 4 h and analyzed by means of gas chromatography for the composition thereof. In this way, the selectivity of the formation of 2-methyl-4-phenyl-2-butanol based on the styrene used was determined. The selectivities are reported in the table which follows:

Styrene [mmol] 40 80 120 160 200 Reaction time [h] 4 8 12 16 20 Pressure [MPa] 20.3 20.7 20.1 18.4 18.4 Selectivity [%] 81.8 71.3 65.1 62.2 58.0

Step b EXAMPLE 5

A 300 ml autoclave was initially charged with 10.2 g of 2-methyl-4-phenyl-2-butanol (62 mmol), dissolved in 150 ml of tetrahydrofuran, and 1.7 g of the catalyst from preparation example 1 in a catalyst basket. The autoclave was purged three times with nitrogen, and then hydrogen was injected to pressure 200 bar at 200° C. for 12 hours.

After 6 and 12 hours, the progress of the reaction was analyzed by means of gas chromatography (30 m, column material DB1, internal diameter: 0.25 mm, film thickness: 0.25 μm, temperature program 50° C.-5 min isothermal; 6° C./min.→290° C.-219 min. isothermal). The product contents are reported in the table which follows.

4-Cyclohexyl- 2-Methyl-4-phenyl- 4-Cyclohexyl- 2-methyl-2-butanol 2-butanol 2-methylbutane  6 hours 88.9% 0% 5.9% 12 hours 88.2% 0% 6.8%

After only 6 h, no starting material was detectable any longer. The low proportion of by-products such as 4-cyclohexyl-2-methylbutane demonstrates the high selectivity of the hydrogenation for the desired target compound 4-cyclohexyl-2-methyl-2-butanol.

EXAMPLE 6

In a 300 mL autoclave, 70 g of 2-methyl-4-phenyl-2-butanol (0.43 mol) were dissolved in 97 g of tetrahydrofuran, and 2.2 g of a catalyst according to preparation example 1 were initially charged in a catalyst basket. The autoclave was purged three times with nitrogen. This was followed by hydrogenation at 160° C. and hydrogen pressure 160 bar for 10 hours. The output was analyzed by means of gas chromatography (30 m column material DB1 ID: 0.25 mm, FD: 0.25 μm, 50° C.-5 min isothermal, −6° C./min→290° C.-219 min isothermal). The composition of the output after 10 h is reported in the table below.

4-Cyclohexyl- 2-Methyl-4-phenyl- 4-Cyclohexyl- 2-methyl-2-butanol 2-butanol 2-methylbutane Comp. 10 h 95.4% 0.0% 4.6% [area %]¹⁾ ¹⁾Composition of the output after 10 h

EXAMPLE 7

A 300 mL autoclave was initially charged with 160 g of 2-methyl-4-phenyl-2-butanol (0.98 mol) and 6.4 g of a catalyst according to example 1 of EP 1042273 (0.5% Ru/Al₂O₃) in a catalyst basket. The autoclave was purged with nitrogen three times. This was followed by hydrogenation at 160° C. and hydrogen pressure 160 bar for 10 hours. The output was analyzed by means of gas chromatography (30 m column material DB1 ID: 0.25 mm, FD: 0.25 μm, 50° C.-5 min isothermal, −6° C./min→290° C.-219 min isothermal). The composition of the output after 10 h is reported in the table below.

4-Cyclohexyl- 2-Methyl-4-phenyl- 4-Cyclohexyl- 2-methyl-2-butanol 2-butanol 2-methylbutane Comp. 10 h 90.1% 0.1% 2.5% [area %] ¹⁾ ¹⁾ Composition of the output after 10 h

EXAMPLE 8

A 300 mL autoclave was initially charged with 160 g of 2-methyl-4-phenyl-2-butanol (0.98 mol) and 0.64 g of a commercially available supported Rh catalyst (Escat 34, from Engelhard-5% Rh/Al₂O₃) in a catalyst basket. The autoclave was purged three times with nitrogen, and this was followed by hydrogenation at 160° C. and hydrogen pressure 160 bar for 10 hours. The output was analyzed by means of gas chromatography (30 m column material DB1 ID: 0.25 mm, FD: 0.25 μm, 50° C.-5 min isothermal, −6° C./min→290° C.-219 min isothermal). The composition of the output after 10 h is reported in the table below.

4-Cyclohexyl- 2-Methyl-4-phenyl- 4-Cyclohexyl- 2-methyl-2-butanol 2-butanol 2-methylbutane Comp. 10 h 92.5% 0.0% 0.25% [area %] ¹⁾ ¹⁾ Composition of the output after 10 h

EXAMPLE 9

A 300 mL autoclave was initially charged with 160 g of 2-methyl-4-phenyl-2-butanol (0.98 mol) and 0.04 g of a commercial nickel catalyst (Ni5249P, from BASF, approx. 65% Ni/SiO₂/MgO). The autoclave was purged three times with nitrogen, and this was followed by hydrogenation at 160° C. and hydrogen pressure 160 bar for 10 hours. The output was analyzed by means of gas chromatography (30 m column material DB1 ID: 0.25 mm, FD: 0.25 μm, 50° C.-5 min isothermal, −6° C./min→290° C.-219 min isothermal). The composition of the output after 10 h is reported in the table below.

4-Cyclohexyl- 2-Methyl-4-phenyl- 4-Cyclohexyl- 2-methyl-2-butanol 2-butanol 2-methylbutane Comp. 10 h 86.9% 4.6% 1.02% [area %] ¹⁾ ¹⁾ Composition of the output after 10 h

EXAMPLE 10

The reaction was conducted in a continuous laboratory plant which comprises a main reactor composed of three series-connected tubular reactors with circulation (main reactor (MR)) and a postreactor (PR) configured as a tubular reactor. The tubular reactors were filled with the catalyst A prepared according to preparation example 1 as follows: MR: each tube 71 g, PR: 3.25 g. The first and third tubes of the main reactor were operated in trickle mode, the second tube in liquid phase mode, and the output of the 3^(rd) tube was partly combined with the feed to the first tube. The postreactor was operated in straight pass in liquid phase mode. 2-Methyl-4-phenyl-2-butanol (20-30 g/h; catalyst hourly space velocity=0.4-0.6 kg/(L×h)) was pumped through the reactor cascade with pure hydrogen at a mean temperature of 120-180° C. in the main reactor and 140-180° C. in the postreactor, and a constant pressure of 36 bar. The conversion of 2-methyl-4-phenyl-2-butanol was 100%, the selectivity for 4-cyclohexyl-2-methyl-2-butanol 88-98%. The samples were analyzed by means of gas chromatography (30 m column material DB1 ID: 0.25 mm, FD: 0.25 μm, 50° C.-5 min isothermal, −6° C./min→290° C.-219 min isothermal). The hydrogenation was conducted over a period of 250 h, without any observable decrease in the catalyst activity.

EXAMPLE 11 Mixture of 4-cyclohexyl-2-methyl-2-butanol and 4-cyclohexyl-2-methyl-2-pentanol

In a 300 mL autoclave, 69 g of a mixture consisting of 2-methyl-4-phenyl-2-butanol (98.2 area %) and 2-methyl-4-phenyl-2-pentanol (0.6 area %) were dissolved in 95 g of tetrahydrofuran, and 2.2 g of a catalyst according to preparation example 1 were initially charged in a catalyst basket. The autoclave was purged three times with nitrogen. This was followed by hydrogenation at 160° C. and hydrogen pressure 160 bar for 10 hours. The output was analyzed by means of gas chromatography (30 m column material DB1 ID: 0.25 mm, FD: 0.25 μm, 50° C.-5 min isothermal, −6° C./min→290° C.-219 min isothermal). The composition of the output after 10 h is reported in the table below.

4-Cyclohexyl- 4-Cyclohexyl- 2-Methyl- 2-Methyl- 4-Cyclohexyl- 2-methyl- 2-methyl- 4-phenyl- 4-phenyl- 2-methyl- 2-butanol 2-pentanol 2-pentanol 2-butanol butane Comp. 10 h 97.4% 0.5% 0.0% 0.0% 1.7% [area %]¹⁾ ¹⁾Composition of the output after 10 h

After distillative removal of 4-cyclohexyl-2-methylbutane, a mixture of 4-cyclohexyl-2-methyl-2-butanol and 4-cyclohexyl-2-methyl-2-pentanol was obtained, which differed from the pure substance 4-cyclohexyl-2-methyl-2-butanol especially by an additional, advantageous, slight flowery note.

EXAMPLE 12 4-Cyclohexyl-2-methyl-2-pentanol

By reaction of α-methylstyrene with isopropanol under the conditions described in example 1, after multistage distillation, a mixture which 2-methyl-4-phenyl-2-pentanol (90.3 GC area %) was obtained. In a 300 mL autoclave, 27.7 g of this mixture were dissolved in 132.3 g of tetrahydrofuran, and 1.6 g of a catalyst according to preparation example 1 were initially charged in a catalyst basket. The autoclave was purged three times with nitrogen. This was followed by hydrogenation at 160° C. and hydrogen pressure 160 bar for 10 hours. The output was analyzed by means of gas chromatography (30 m column material DB1 ID: 0.25 mm, FD: 0.25 μm, 50° C.-5 min isothermal, −6° C./min 290° C.-219 min isothermal). The composition of the output after 10 h is reported in the table below.

4-Cyclohexyl- 2-Methyl-4-phenyl- 2-methyl-2-pentanol 2-pentanol Comp. 10 h 85.9% 1.4% [area %]¹⁾ ¹⁾Composition of the output after 10 h

4-Cyclohexyl-2-methyl-2-pentanol by means of high-resolution mass spectrometry (HRMS) and by means of ¹H NMR identified:

HRMS (GC-ToF-MS, FI):

[M-H₂O+H]+166,1726 (measured);

[M-H₂O+H]+166,1722 (calculated for C₁₂H₂₂) difference+0.0004

¹H NMR (400 MHz, d⁶-dmso): δ=4.05 (s, 1H), 2.48 (s, 2H), 0.95-1.77 (m, 12H), 1.05 (s, 6H), 0.92 (d, 3H) ppm. 

1-35. (canceled)
 36. A composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol.
 37. The composition according to claim 36, in which the weight ratio of 2-methyl-4-phenyl-2-butanol to 2-methyl-phenyl-2-pentanol is in the range from 50:1 to 1000:1.
 38. A process for preparing the composition according to claim 36, the process comprising reacting styrene with isopropanol at elevated temperature under conditions under which isopropanol is present under supercritical conditions, the molar ratio of styrene to isopropanol being in the range from 1:10 to 1:130.
 39. The process according to claim 38, wherein at least 80% of the isopropanol is initially charged and at least 80% of the styrene is supplied to the reaction under reaction conditions.
 40. A fragrance which comprises 2-methyl-4-phenyl-2-pentanol or the composition according to claim
 36. 41. A cosmetic composition which comprises 2-methyl-4-phenyl-2-pentanol or the composition according to claim
 36. 42. A washing or cleaning composition which comprises 2-methyl-4-phenyl-2-pentanol or the composition according to claim
 36. 43. 4-Cyclohexyl-2-methyl-2-pentanol.
 44. A process for preparing 4-cyclohexyl-2-methyl-2-pentanol, comprising the heterogeneously catalyzed hydrogenation of 2-methyl-4-phenyl-2-pentanol over a catalyst suitable for ring hydrogenation of aromatics.
 45. The process according to claim 44, comprising a′) preparing a composition comprising 2-methyl-4-phenyl-2-butanol and 2-methyl-4-phenyl-2-pentanol by reaction of styrene with isopropanol at elevated temperature under conditions under which isopropanol is present under supercritical conditions, the molar ratio of styrene to isopropanol being in the range from 1:10 to 1:130; b′) heterogeneously catalyzed hydrogenation of the composition obtained in step a′) over a catalyst suitable for ring hydrogenation of aromatics; and c) distillative workup of the composition obtained in step b′) to obtain a composition consisting essentially of 4-cyclohexyl-2-methyl-2-pentanol; or c′) distillative workup of the composition obtained in step a′) to obtain a composition consisting predominantly of 2-methyl-4-phenyl-2-pentanol and b′) heterogeneously catalyzed hydrogenation of the composition obtained in step c) over a catalyst suitable for ring hydrogenation of aromatics; and optionally c″) distillative workup of the composition obtained in step b′) to obtain a composition consisting essentially of 4-cyclohexyl-2-methyl-2-pentanol.
 46. The process according to claim 44, comprising: a″) reacting a-methylstyrene with isopropanol at elevated temperature to obtain 2-methyl-4-phenyl-2-pentanol, and b″) heterogeneously catalyzed hydrogenation of 2-methyl-4-phenyl-2-pentanol over a catalyst suitable for ring hydrogenation of aromatics.
 47. A composition comprising 4-cyclohexyl-2-methyl-2-pentanol.
 48. The composition as claimed in claim 47 which additionally comprises 4-cyclohexyl-2-methyl-2-butanol.
 49. The composition according to claim 48, in which the weight ratio of 4-cyclohexyl-2-methyl-2-butanol to 4-cyclohexyl-2-methyl-2-pentanol is in the range from 50:1 to 1000:1.
 50. A fragrance which comprises the composition according to claim
 47. 51. A cosmetic composition which comprises the composition according to claim
 47. 52. A washing or cleaning composition which comprises the composition according to claim
 47. 53. A fragrance which comprises the 4-Cyclohexyl-2-methyl-2-pentanol according to claim
 43. 54. A cosmetic composition which comprises the 4-Cyclohexyl-2-methyl-2-pentanol according to claim
 43. 55. A washing or cleaning composition which comprises the 4-Cyclohexyl-2-methyl-2-pentanol according to claim
 43. 